WO1982001877A1 - A process for advancing epoxy resins in molecular weight and a process for preparing resin impregnated substrates - Google Patents
A process for advancing epoxy resins in molecular weight and a process for preparing resin impregnated substrates Download PDFInfo
- Publication number
- WO1982001877A1 WO1982001877A1 PCT/US1981/001590 US8101590W WO8201877A1 WO 1982001877 A1 WO1982001877 A1 WO 1982001877A1 US 8101590 W US8101590 W US 8101590W WO 8201877 A1 WO8201877 A1 WO 8201877A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxide
- epoxy resin
- catalyst
- employed
- resin
- Prior art date
Links
- 0 CON*1(*)CC1 Chemical compound CON*1(*)CC1 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2363/00—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Definitions
- Epoxy resins have heretofore been advanced in the presence of phosphonium catalysts disclosed by Dante in U.S. 3,477,990 and Perry in Canadian 893,191 and U.S. 3,948,855.
- the quantities of catalyst employed were that which would provide a resin having a percent epoxide value sufficiently close to the theoretical epoxide value that no improvement in properties were envisioned.
- the process of the present invention provides for the production of advanced epoxy resins having an improvement in one or more physical properties such as, for example, reactivity or glass transition temperature of the cured resins.
- Resins having faster reactivity characteristics provide for increased productivity of articles produced therefrom over a unit time period.
- the increase in glass transition temperature of a cured resin permits articles prepared therefrom to be employed in higher temperature environments.
- Cured epoxy resins having increased glass transition temperatures provide products which can be employed in environments of higher temperatures i . e . , the useful operating temperature is generally directly proportional to the glass transition temperature.
- the present invention pertains to a process for advancing epoxy resins in molecular weight by reacting (A) an epoxy resin which is a glycidyl ether of a dihydric phenol having an average of more than one glycidyl ether group per molecule with (B) a dihydric phenolic compound in the presence of (C) a phosphonium catalyst employing components (A) and (B) in quantities such that the phenolic hydroxyl to epoxide equivalent ratio is that which will provide a theoretical percent epoxide of the resultant reaction product of from 2.7 to 14, preferably from 7 to 12.5; characterized by employing the catalyst, component (C), in a quantity such that the epoxy resin which would result when subjecting a mixture of components (A), (B) and (C) to suitable reaction conditions produces an advanced epoxy resin wherein the difference obtained by subtracting the percent epoxide obtained by analysis from the theoretical percent epoxide is from 0.5 to 4, preferably from 1 to 2.
- the present invention also pertains to products resulting from curing a mixture of an epoxy resin prepared by the above procedure and a curing quantity of a curing agent therefor.
- the present invention also pertains to a process for preparing resin impregnated substrates for use in preparing electrical laminates by a process which comprises: (I) saturating said substrate with a resin forming mixture comprising;
- a glycidyl ether of a dihydric phenol having an average of more than one epoxide group per molecule and an epoxide equivalent weight (EEW) of from 156 to 400, preferably from 177 to 190, with
- a phosphonium catalyst for effecting the reaction between (1) and (2), wherein components ( 1 ) and (2 ) are employed in quantities which will provide a theoretical percent epoxide of the reaction product of from 8 to 15, preferably from 9.5 to 13;
- Suitable glycidyl ethers of a dihydric phenol which can be employed in the present invention include those represented by the formula
- A is a divalent hydrocarbon group having from 1
- each X is independently hydrogen, chlorine or bromine; x has a value of zero or one and n has a value such that the EEW is from 156 to 400, preferably from 177 to 190, calculated on the basis of X being hydrogen.
- Particularly suitable are the diglycidyl ethers of bisphenol A and tetrabromobisphenol A.
- Suitable dihydric phenolic compounds include, for example, catechol, hydroquinone, resorcinol and bisphenols such as those represented by the formula
- dihydric phenolic compounds are bisphenol A and tetrabromobisphenol A.
- Suitable phosphonium catalysts which can be employed herein include, for example, those compounds having at least one phosphonium cation group represented by the formula
- each R is independently a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20, preferably from 1 to 6, carbon atoms or substituted hydrocarbyl groups. It is preferred that at least one, preferably two and most preferably three, of the R groups be an aromatic group i.e., an aryl group or an alkaryl group such that the phosphorus atom is attached directly to the aromatic ring of such aryl or alkaryl group.
- hydrocarbyl it is meant that the groups can be alkyl, aryl, alkaryl, aralkyl and the alkyl can be either cyclic or acyclic.
- substituted hydrocarbyl it is meant that the hydrocarbyl groups can contain one or more inert substituent groups such as, for example, Cl, Br, I, NO 2 , or mixtures thereof.
- the R groups can contain any substituent group which is inert to the system, i.e. will not deactivate the catalyst under the conditions in which they are employed.
- the phosphonium cation contain at least one aromatic ring and at least one alkyl group attached directly to a phosphorous atom.
- Suitable anions include the halides, such as, for example, Cl, Br, I, carboxylates, dicarboxylates, phosphates, nitrates, sulfates, nitrites, sulfites, borates, chromates, or mixtures thereof.
- the preferred anions are the strong acids, i.e. those having a pK value less than 4.5, preferably less than 3.7, because the catalysts containing such are generally more efficient, in that it takes less catalyst to effect the lowering of the epoxide value to the desired value below the theoretical value.
- the dihydric phenol and the glycidyl ether of a dihydric phenol are employed in quantities such that the theoretical percent epoxide of the resultant product is from 2.7 to 14, preferably from 7 to 12.5.
- the quantity of catalyst will of course vary depending upon the particular catalyst employed; however, for most catalysts, from 0.1 to 1.5, preferably from 0.2 to 0.8, parts catalyst by weight per 100 parts by weight of glycidyl ether of dihydric phenol can be employed.
- the reaction conditions employed to prepare the advanced epoxy resins can vary, but temperatures of from 100°C to 200°C, preferably from 120°C to 160°C, are suitable. Lower temperatures usually require longer reaction times whereas higher temperatures usually require shorter reaction times.
- the pressure employed is not particularly important and can be from 1 mm Hg vacuum (0.13 kPa) to 100 psig (791 kPa). However, it is usually preferred to employ pressures of from 5 psig (136 kPa) to 20 psig (239 kPa).
- reaction conditions are not important so long as for the particular phosphonium catalyst and quantity thereof employed, the reaction conditions produce the desired result i.e., the resultant advanced epoxy resin has the required difference between the theoretical percent epoxide and the actual percent epoxide value obtained by analysis.
- curing agents can be employed in the present invention to cure the epoxy resins.
- curing agents include amines, amides, guanidines, phenolic hydroxyl-containing materials, carboxylic acids, carboylic acid anhydrides, imidazoles, biguanides, or mixtures thereof.
- Particulary suitable curing agents include, for example, guanidines such as for example, dicyandiatiide and tetramethyl guanidine and biguanides such as 1,6-xylene biguanide, polyhydric phenols, or mixtures thereof.
- guanidines such as for example, dicyandiatiide and tetramethyl guanidine
- biguanides such as 1,6-xylene biguanide, polyhydric phenols, or mixtures thereof.
- the quantity of curing agent employed depends upon the particular curing agent employed and the propertied desired in the resultant cured resin, all of which is well known by those persons reasonably skilled in the art and discussed in HANDBOOK OF EPOXY RESINS, by Lee and Neville, McGraw Hill, 1967.
- EqER epoxide equivalents from the epoxy resin.
- EqDHP phenolic hydroxyl equivalents from the dihydric phenol.
- WtER weight of epoxy resin employed.
- WtDHP weight of dihydric phenol employed.
- the actual percent epoxide was determined experimentally by titration with perchloric acid in glacial acetic acid by the liberation of hydrogen bromide generated by the addition of tetraethylammonium bromide in glacial acetic acid using crystal violet as an indicator.
- the epoxy groups react stoichiometrically with hydrogen bromide generated from the reaction of perchloric acid with tetraethyl ammonium bromide. When the epoxy groups have been reacted, the free hydrogen bromide causes the crystal violet to change color.
- the glass transition temperature, Tg was determined by the method of ASTM D3418-75 on cured specimens prepared in the following manner. A mixture of 10 grams of the resultant epoxy resin, 0.3 gram of dicyanandiamide and 0.01 gram of 2-methyl imidazole was melt mixed on a 100°C hot plate for 3 minutes. The mixture was finely ground in a mortar and pestle. The powder was transferred to an aluminum weighing dish and cured at 175°C for 2 hours.
- the stroke cure reactivity was determined by the following procedure.
- An acetone solution of epoxy resin is prepared by blending 10 grams of acetone with 30 grams of molten epoxy resin warmed to between 80°C and 100°C. The solution is allowed to cool to room temperature and then 9 grams of a 10 percent solution of dicyandiamide in the monomethylether of ethylene glycol and 0.75 gram of a 10 percent solution of benzyldimethylamine (BDMA) in acetone is added (3 phr dicyandiamide, 0.25 phr BDMA). The solution is mixed well and allowed to stand at room temperature for a period of 2 hours. The catalyzed resin is then drawn in an eye dropper and placed on a hotplate at 175°C ⁇ 1°C. The stop watch is immediately started.
- BDMA benzyldimethylamine
- the sample is allowed to rest on the hotplate undisturbed for 60 ⁇ 1 seconds. At this point, begin stroking with a wooden spatula. Stroking should be done by pushing the resin puddle back and forth over an area about 1 square inch using the same side of the spatula in contact with the resin. The resin will thicken as it is continuously stroked. Eventually the resin will become stringy and immediately after, becomes a rubber gel that releases from the hotplate. This is the end point. Stop the stopwatch and record the reading. The fewer the number of seconds, the higher the reactivity.
- the particular precursor As a 70 percent solution in methanol.
- the particular acid employed was slowly added to the solution while swirling the flask.
- the solvent and excess acetic acid were removed under vacuum while heating to a final temperature of 120°C at 1 mm Hg (0.13 kPa).
- the resultant product was acetone washed thereby yielding the phosphonium salt of the acid employed.
- a methanol slurry of 65 g (70 percent by weight H 2 O) of an anion exchange resin in the acetate form (200-400 mesh; .8 meq. per ml resin bed; 3.5 meq. per dry gram; 70 to 78 wt. percent moisture; styrene type quaternary ammonium; wet mesh range 80-200) available from BIO. RAD Laboratories as AG1-X2.
- a 5 percent solution in methanol of potassium hydroxide was slowly eluded through the column at a rate of 2 drops per second. The column was then washed with methanol until neutral to litmus paper.
- the phosphonium catalyst precursor as a 70 percent solution in methanol, was then added to the column and slowly eluded through the ion exchange resin until the dark band was washed through the column.
- the eluded material was caught in a RBF containing an excess molar ratio of the acid. This solution was then rotoevaporated and acetone washed to yield a white solid phosphonium salt of the acid.
- BTPP butyltriphenylphosphonium
- ClAc chloroacetate
- ETPP ethyltriphenylphosphonium
- Epoxy Resin A was a liquid diglycidyl ether of bisphenol A having an average epoxide equivalent weight of 189, percent epoxide of 22.75 percent and an aliphatic chloride content of 3410 ppm.
- Epoxy Resin B was a liquid diglycidyl ether of bisphenol A having an average epoxide equivalent weight of 188, percent epoxide of 22.82 percent and an aliphatic chloride content of 3700 ppm.
- Epoxy Resin C was a liquid diglycidyl ether of bisphenol-A having an average epoxide equivalent weight of 186.5, percent epoxide of 23.06 and an aliphatic chloride content of 2200 parts per million.
- Dihydric phenol A was tetrabromobisphenol A having a phenolic hydroxyl equivalent weight of 272 and percent bromine content of 58.8 percent.
- DIHYDRIC PHENOL B
- Dihydric phenol B was a bisphenol A having a phenol hydroxyl equivalent weight of 114.
- a prepreg varnish formulation was prepared by blending 5411 g of a 75 percent solution by weight in acetone of the resin of example #22 with 1225 g of a 10 percent solution of dicyandiamide in the monomethylether of ethylene glycol ( ⁇ 3 phr dicyandiamide), 6.13 g of benzyldimethylamine ( ⁇ 0.15 phr BDMA) and 200 g acetone.
- the viscosity of the solution at 25°C was 25 seconds using a #2 Zahn cup.
- the 175°C stroke cure reactivity of the prepreg varnish was about 245 seconds.
- Fiberglass cloth (type 7628 with 1399 finish) was impregnated by passing it through the prepreg varnish described in A above, followed by a pair of doctor bars set at 15 mils (0.38 mm) clearance to control resin pickup, and finally through an oven at 300°F (149°C) for a dwell time of approximately 4 minutes.
- the resulting B-staged impregnated cloth of prepreg had a gel time of 93 seconds at 175°C.
- a laminate was then prepared from the above prepared preimpregnated fiberglass employing 6 plys of 12 in. ⁇ 12 in. ⁇ 0.13 in. (3 cm ⁇ 3 cm ⁇ .33 mm) sheets of 7628 style glass all of which were 1399 finish.
- the laminate was prepared by pressing at 500 psig (3549 kPa) for 60 minutes at 175°C. The laminate was then tested.
- the pressure cooker-solder test was conducted by (i) cutting 2 in. x 4 in. (5 cm ⁇ 10 cm) coupons from prepared laminate, (ii) placing 3 coupons edgewise on a rack in a pressure cooker and maintaining 15 psig (205 kPa) steam pressure for ⁇ 1.5 hour, and
- the laminate had a glass transition temperature (Tg) of 130°C. After subjecting to 15 psig (205 kPa) steam pressure for 1-1/2 hours and immersion in 500°F (260°C) solder for 20 seconds, 5-1/2 sides of the laminate out of six sides passed the test.
- Tg glass transition temperature
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR8108901A BR8108901A (pt) | 1980-12-04 | 1981-12-01 | Processo para aumentar o peso molecular de resinas epoxi e processo para preparar substratos impregnados com a resina |
DE8282900270T DE3177033D1 (en) | 1980-12-04 | 1981-12-01 | A process for advancing epoxy resins in molecular weight and a process for preparing resin impregnated substrates |
DK325482A DK325482A (da) | 1980-12-04 | 1982-07-20 | Fremgangsmaade til avancering af epoxyharpikser i molekylvaegt og en fremgangsmaade til fremstilling af harpiksimpraegnerede substrater |
NO82822632A NO158103C (no) | 1980-12-04 | 1982-08-02 | Fremgangsmaate for aa forhoeye epoksyharpiksers molekylvekt,samt fremgangsmaate for fremstilling av harpiksimpregnerteunderlag ved anvendelse av den resulterende harpiks. |
SG754/89A SG75489G (en) | 1980-12-04 | 1989-11-23 | A process for advancing epoxy resins in molecular weight and a process for preparing resin impregnated substrates |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/212,959 US4352918A (en) | 1980-12-04 | 1980-12-04 | Process for preparing epoxy resins having improved physical properties when cured using quaternary phosphonium catalysts |
US212959801204 | 1980-12-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1982001877A1 true WO1982001877A1 (en) | 1982-06-10 |
Family
ID=22793129
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1981/001590 WO1982001877A1 (en) | 1980-12-04 | 1981-12-01 | A process for advancing epoxy resins in molecular weight and a process for preparing resin impregnated substrates |
Country Status (14)
Country | Link |
---|---|
US (1) | US4352918A (es) |
EP (1) | EP0065573B1 (es) |
JP (2) | JPH0219132B2 (es) |
AU (1) | AU544845B2 (es) |
BE (1) | BE891363A (es) |
BR (1) | BR8108901A (es) |
CA (1) | CA1167197A (es) |
DE (1) | DE3177033D1 (es) |
DK (1) | DK325482A (es) |
ES (1) | ES507678A0 (es) |
IT (1) | IT1172128B (es) |
NO (1) | NO158103C (es) |
SG (1) | SG75489G (es) |
WO (1) | WO1982001877A1 (es) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0099334A1 (de) * | 1982-07-08 | 1984-01-25 | Ciba-Geigy Ag | Verfahren zur Herstellung von Epoxidharzen nach dem Advancementverfahren |
WO1986001216A1 (en) * | 1984-08-16 | 1986-02-27 | The Dow Chemical Company | Epoxy resins of controlled conversion and a process for their preparation |
EP0187855A1 (en) * | 1984-07-17 | 1986-07-23 | Dow Chemical Co | PARTLY PROMOTED EPOXY RESIN COMPOSITIONS AND PRODUCTS PRODUCED BY THEIR REACTION AND NETWORKING. |
EP0193809A2 (en) * | 1985-02-26 | 1986-09-10 | The Dow Chemical Company | Solventless process for producing resinous materials |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4389520A (en) * | 1982-04-05 | 1983-06-21 | Ciba-Geigy Corporation | Advancement catalysts for epoxy resins |
US4496709A (en) * | 1982-06-23 | 1985-01-29 | The Dow Chemical Company | Process for preparing epoxy resins employing a phosphonium trifluoroacetate catalyst |
WO1984000171A1 (en) * | 1982-06-23 | 1984-01-19 | Dow Chemical Co | Process for preparing advanced epoxy resins employing a phosphonium trifluoroacetate catalyst |
US4438254A (en) * | 1983-02-28 | 1984-03-20 | The Dow Chemical Company | Process for producing epoxy resins |
US4634757A (en) * | 1985-07-15 | 1987-01-06 | Shell Oil Company | Fusion product |
US4692504A (en) * | 1986-04-30 | 1987-09-08 | Shell Oil Company | Deactivation of phosphonium salt catalyst |
US4732958A (en) * | 1986-12-30 | 1988-03-22 | Shell Oil Company | Epoxy fusion process |
US4829141A (en) * | 1987-07-31 | 1989-05-09 | Shell Oil Company | Epoxy fusion catalyst and process |
US4933420A (en) * | 1988-09-23 | 1990-06-12 | The Dow Chemical Company | Epoxy resins containing phosphonium catalysts |
US4996279A (en) * | 1988-10-07 | 1991-02-26 | Shell Oil Company | Dissymmetric polymer materials |
US5310854A (en) * | 1989-08-23 | 1994-05-10 | The Dow Chemical Company | Epoxy resin composition and process therefor |
US4981926A (en) * | 1990-02-06 | 1991-01-01 | The Dow Chemical Company | Composition of epoxy resin, amino group-containing phosphonium catalyst and curing agent |
US5208317A (en) * | 1990-02-06 | 1993-05-04 | The Dow Chemical Company | Composition comprising epoxy resin and cationic amine phosphonium catalyst |
GB9027406D0 (en) * | 1990-12-18 | 1991-02-06 | Ciba Geigy Ag | Production of compounds |
JPH059394A (ja) * | 1991-03-29 | 1993-01-19 | Dainippon Ink & Chem Inc | 難燃性合成樹脂組成物及び難燃剤 |
US5202407A (en) * | 1992-01-24 | 1993-04-13 | The Dow Chemical Company | Precatalyzed catalyst compositions, process for preparing epoxy resins curable compositions, articles resulting from curing the resultant compositions |
DE19714432C2 (de) * | 1997-04-08 | 2000-07-13 | Aventis Res & Tech Gmbh & Co | Trägerkörper mit einer Schutzbeschichtung und Verwendung des beschichteten Trägerkörpers |
WO2018165090A1 (en) | 2017-03-09 | 2018-09-13 | Carbon, Inc. | Tough, high temperature polymers produced by stereolithography |
EP3849806B1 (en) | 2018-09-10 | 2023-04-05 | Carbon, Inc. | Dual cure additive manufacturing resins for production of flame retardant objects |
WO2020205212A1 (en) | 2019-03-29 | 2020-10-08 | Carbon, Inc. | Dual cure resin for the production of moisture-resistant articles by additive manufacturing |
WO2022066565A1 (en) | 2020-09-25 | 2022-03-31 | Carbon, Inc. | Epoxy dual cure resin for the production of moisture-resistant articles by additive manufacturing |
Citations (18)
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US3306872A (en) * | 1961-10-16 | 1967-02-28 | Shell Oil Co | Method for producing a polyether resin |
US3477990A (en) * | 1967-12-07 | 1969-11-11 | Shell Oil Co | Process for reacting a phenol with an epoxy compound and resulting products |
US3480471A (en) * | 1965-05-22 | 1969-11-25 | Ciba Ltd | Process for the manufacture of pre-impregnated webs |
CA893191A (en) * | 1972-02-15 | The Dow Chemical Company | Process for reacting a phenol with a vicinal epoxy compound | |
US3679465A (en) * | 1970-10-23 | 1972-07-25 | Ciba Geigy Corp | Process for producing hardenable epoxy resin compositions |
US3687894A (en) * | 1970-07-23 | 1972-08-29 | William G Collings | A composition of a liquid epoxy resin, a polyhydroxyl material and a hardener |
US3738862A (en) * | 1971-11-08 | 1973-06-12 | Shell Oil Co | Process for preparing reinforced laminates in situ with epoxy-polyhydric phenol condensates |
US3931109A (en) * | 1972-03-13 | 1976-01-06 | The Dow Chemical Company | Process for coating substrates with high molecular weight epoxy resins |
US3948855A (en) * | 1971-09-16 | 1976-04-06 | The Dow Chemical Company | Process for reacting a phenol with a vicinal epoxy compound in the presence of phosphorus or carbon containing acid, ester or acid ester |
GB1434889A (en) * | 1973-04-09 | 1976-05-05 | Mitsubishi Chem Ind | Electrical insulating prepreg |
US3998983A (en) * | 1975-06-27 | 1976-12-21 | Westinghouse Electric Corporation | Resin rich epoxide-mica flexible high voltage insulation |
US4075260A (en) * | 1971-08-05 | 1978-02-21 | General Electric Company | Epoxy resin compositions and laminate made therewith |
US4093650A (en) * | 1976-04-23 | 1978-06-06 | The Dow Chemical Company | Process for preparing trihydrocarbyl (2,5-dihydroxyphenyl) phosphonium salts |
US4132706A (en) * | 1974-06-21 | 1979-01-02 | The Dow Chemical Company | Latent catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids |
US4168331A (en) * | 1978-08-03 | 1979-09-18 | The Dow Chemical Company | Process for preparing resin impregnated substrates for use in preparing electrical laminates |
US4171420A (en) * | 1974-06-21 | 1979-10-16 | The Dow Chemical Company | Latent catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids |
US4177216A (en) * | 1974-06-21 | 1979-12-04 | The Dow Chemical Company | Novel tributyl (2,5-dihydroxyphenyl)phosphonium hydroxide inner salts |
US4251594A (en) * | 1979-09-27 | 1981-02-17 | The Dow Chemical Company | Process for preparing resin impregnated substrates for use in preparing electrical laminates |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1494971A (en) * | 1976-01-19 | 1977-12-14 | Dow Chemical Co | Epoxy resin compositions |
-
1980
- 1980-12-04 US US06/212,959 patent/US4352918A/en not_active Expired - Lifetime
-
1981
- 1981-12-01 DE DE8282900270T patent/DE3177033D1/de not_active Expired
- 1981-12-01 JP JP57500333A patent/JPH0219132B2/ja not_active Expired - Lifetime
- 1981-12-01 AU AU80050/82A patent/AU544845B2/en not_active Ceased
- 1981-12-01 WO PCT/US1981/001590 patent/WO1982001877A1/en active IP Right Grant
- 1981-12-01 BR BR8108901A patent/BR8108901A/pt not_active IP Right Cessation
- 1981-12-01 EP EP82900270A patent/EP0065573B1/en not_active Expired
- 1981-12-03 CA CA000391461A patent/CA1167197A/en not_active Expired
- 1981-12-03 ES ES507678A patent/ES507678A0/es active Granted
- 1981-12-04 BE BE0/206749A patent/BE891363A/fr not_active IP Right Cessation
- 1981-12-04 IT IT49839/81A patent/IT1172128B/it active
-
1982
- 1982-07-20 DK DK325482A patent/DK325482A/da not_active Application Discontinuation
- 1982-08-02 NO NO82822632A patent/NO158103C/no unknown
-
1983
- 1983-12-09 JP JP58232644A patent/JPS59149930A/ja active Granted
-
1989
- 1989-11-23 SG SG754/89A patent/SG75489G/en unknown
Patent Citations (18)
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CA893191A (en) * | 1972-02-15 | The Dow Chemical Company | Process for reacting a phenol with a vicinal epoxy compound | |
US3306872A (en) * | 1961-10-16 | 1967-02-28 | Shell Oil Co | Method for producing a polyether resin |
US3480471A (en) * | 1965-05-22 | 1969-11-25 | Ciba Ltd | Process for the manufacture of pre-impregnated webs |
US3477990A (en) * | 1967-12-07 | 1969-11-11 | Shell Oil Co | Process for reacting a phenol with an epoxy compound and resulting products |
US3687894A (en) * | 1970-07-23 | 1972-08-29 | William G Collings | A composition of a liquid epoxy resin, a polyhydroxyl material and a hardener |
US3679465A (en) * | 1970-10-23 | 1972-07-25 | Ciba Geigy Corp | Process for producing hardenable epoxy resin compositions |
US4075260A (en) * | 1971-08-05 | 1978-02-21 | General Electric Company | Epoxy resin compositions and laminate made therewith |
US3948855A (en) * | 1971-09-16 | 1976-04-06 | The Dow Chemical Company | Process for reacting a phenol with a vicinal epoxy compound in the presence of phosphorus or carbon containing acid, ester or acid ester |
US3738862A (en) * | 1971-11-08 | 1973-06-12 | Shell Oil Co | Process for preparing reinforced laminates in situ with epoxy-polyhydric phenol condensates |
US3931109A (en) * | 1972-03-13 | 1976-01-06 | The Dow Chemical Company | Process for coating substrates with high molecular weight epoxy resins |
GB1434889A (en) * | 1973-04-09 | 1976-05-05 | Mitsubishi Chem Ind | Electrical insulating prepreg |
US4132706A (en) * | 1974-06-21 | 1979-01-02 | The Dow Chemical Company | Latent catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids |
US4171420A (en) * | 1974-06-21 | 1979-10-16 | The Dow Chemical Company | Latent catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids |
US4177216A (en) * | 1974-06-21 | 1979-12-04 | The Dow Chemical Company | Novel tributyl (2,5-dihydroxyphenyl)phosphonium hydroxide inner salts |
US3998983A (en) * | 1975-06-27 | 1976-12-21 | Westinghouse Electric Corporation | Resin rich epoxide-mica flexible high voltage insulation |
US4093650A (en) * | 1976-04-23 | 1978-06-06 | The Dow Chemical Company | Process for preparing trihydrocarbyl (2,5-dihydroxyphenyl) phosphonium salts |
US4168331A (en) * | 1978-08-03 | 1979-09-18 | The Dow Chemical Company | Process for preparing resin impregnated substrates for use in preparing electrical laminates |
US4251594A (en) * | 1979-09-27 | 1981-02-17 | The Dow Chemical Company | Process for preparing resin impregnated substrates for use in preparing electrical laminates |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0099334A1 (de) * | 1982-07-08 | 1984-01-25 | Ciba-Geigy Ag | Verfahren zur Herstellung von Epoxidharzen nach dem Advancementverfahren |
EP0187855A1 (en) * | 1984-07-17 | 1986-07-23 | Dow Chemical Co | PARTLY PROMOTED EPOXY RESIN COMPOSITIONS AND PRODUCTS PRODUCED BY THEIR REACTION AND NETWORKING. |
EP0187855A4 (en) * | 1984-07-17 | 1987-01-20 | Dow Chemical Co | PARTLY PROMOTED EPOXY RESIN COMPOSITIONS AND PRODUCTS PRODUCED BY THEIR REACTION AND NETWORKING. |
WO1986001216A1 (en) * | 1984-08-16 | 1986-02-27 | The Dow Chemical Company | Epoxy resins of controlled conversion and a process for their preparation |
EP0193809A2 (en) * | 1985-02-26 | 1986-09-10 | The Dow Chemical Company | Solventless process for producing resinous materials |
EP0193809A3 (en) * | 1985-02-26 | 1987-01-28 | The Dow Chemical Company | Solventless process for producing resinous materials |
Also Published As
Publication number | Publication date |
---|---|
ES8303469A1 (es) | 1983-02-01 |
IT1172128B (it) | 1987-06-18 |
JPS59149930A (ja) | 1984-08-28 |
AU8005082A (en) | 1982-06-17 |
US4352918A (en) | 1982-10-05 |
JPH0219132B2 (es) | 1990-04-27 |
EP0065573A4 (en) | 1983-04-06 |
EP0065573A1 (en) | 1982-12-01 |
NO158103B (no) | 1988-04-05 |
NO158103C (no) | 1988-07-13 |
NO822632L (no) | 1982-08-02 |
DE3177033D1 (en) | 1989-05-24 |
IT8149839A0 (it) | 1981-12-04 |
AU544845B2 (en) | 1985-06-13 |
JPS57501861A (es) | 1982-10-21 |
CA1167197A (en) | 1984-05-08 |
ES507678A0 (es) | 1983-02-01 |
JPH0251449B2 (es) | 1990-11-07 |
EP0065573B1 (en) | 1989-04-19 |
SG75489G (en) | 1990-04-20 |
BE891363A (fr) | 1982-06-04 |
DK325482A (da) | 1982-07-20 |
BR8108901A (pt) | 1982-10-26 |
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